Method for equilibrating polyamide magnet wire coatings and enamel compositions

ABSTRACT

A magnet wire enamel based on polyamide resins is disclosed in which the molecular weight of the polyamide resin is reduced through an equilibration reaction with a solvolytic agent and a titanate catalyst. Also disclosed is a method of applying said enamel to a magnet wire substrate and the resulting enameled magnet wire.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 945,159 filed on Dec. 22,1986, now U.S. Pat. No. 4,716,190.

This application relates to commonly assigned, U.S. patent applicationSer. No. 945,160 now U.S. Pat. No. 4,725,458, for URETHANE MODIFIEDNYLON MAGNET WIRE ENAMEL by J. J. Harber filed on even date herewith.

TECHNICAL FIELD

The field of art to which this invention pertains is the equilibrationof polyamide resins and in particular the preparation of polyamide foruse in magnet wire coatings.

BACKGROUND ART

Nylon and other conventional polyamide resins are used throughout themagnet wire industry for the purpose of insulating the wire, either as asolecoat construction (the only insulating layer) or a topcoat appliedover a basecoat enamel, e.g. polyester, polyurethane, etc. In using suchpolyamide resins in this way, a number of problems arise during theirapplication. In particular, it is noted that the available polyamideresins have very high molecular weights, typically ranging from about18,000 to about 40,000 molecular weight units (weight average). Thesehigh molecular weight materials mean that a resulting solution of thismaterial at a high solids content (greater than 17 percent by weight ofsolids) can have a viscosity at room temperature (about 77° F.) of about4,000 centipoises to about 11,000 centipoises. Since the typical enamelor coating which may be easily applied to magnet wire has a viscosity ofabout 50 centipoises to about 2000 centipoises at applicationtemperature greater than 100° F. (37.8° C.). The ability to prepare anacceptable high solids enamel using this nylon is not practical. Thesepolyamide solutions are often prepared having very low solids contentsof about 5 percent to about 16 percent by weight of solids. This lowersthe viscosity to a level which is within the working range of the magnetwire enamel applicators.

Unfortunately, this reduction in solids content means that more diluentmust be used resulting in an added cost to production and an increase inenvironmental pollutants. In addition, the lower solids content can meanmore passes for the wire through the coating are required to apply thedesired coating thickness onto the wire, again adding cost to the wireproduction.

It is known that the molecular weight and thereby the viscosity of thepolyamide resin coatings may be reduced by equilibrating the resin.Equilibration, as used in this application, refers to the solvolyticmolecular weight reduction of a polymer. A common equilibration processwhich is used requires the reaction of monoethanolamine with thepolyamide resin as shown in reaction 1 below: ##STR1## This reactionrequires that an excess of monoethanolamine be present during thereaction. The excess must be neutralized prior to the coating beingapplied to the wire and is accomplished by adding acetic anhydride tothe solution which reacts with the monoethhanolamine in the primaryreaction as shown in reaction 2 below: ##STR2## However certainadditional side reactions also occur during this neutralization process,the most important of which is shown below in reaction 3. ##STR3## Thisreaction being reversible at relatively low temperatures (about 80° C.to about 100° C.) means that during the oven curing of the coating(which temperatures exceed those to reverse the reaction) acetic acidand monoethanolamine are produced. The acetic acid is easily volatilizedout of the coating during curing but the ethanolamine is not completelyremoved and remains behind. This material is known to be deleterious tomany wire varnish curing mechanisms. Therefore, the use of this nylon asa wire coating (particularly for fine wire) results in wire havingundercured coatings which do not effectively adhere to the wire or towire whose mechanical and electrical properties are prematurely reducedduring use.

In addition, the resulting wire coatings do not exhibit uniformproperties from batch to batch and quality control is difficult. Oneevidence of this is the fluctuation in the mandrel pull test used totest the ability of wire coating to withstand numerous cycles of bendingabout a mandrel without exhibiting cracks or defects in the wirecoating. Coatings formed using the conventional monoethanolamineapproach to preparing the equilibrated polyamide exhibits widefluctuations in its ability to pass such tests and in many instances thewire is unacceptable.

Therefore, what is needed in the art is a method by which the polyamideresin may be equilibrated without the introduction or resultingbyproducts which will affect the quality of the final coated wireproduct.

DISCLOSURE OF INVENTION

Disclosed is a method for equilibrating a polyamide resin by reacting atelevated temperatures, a polyamide with a solvolytic agent in thepresence of a titanium catalyst to reduce the average molecular weightof the polyamide resin and therefore, its viscosity.

Also disclosed is a magnet wire substrate having at least one layer ofelectrically insulating enamel which is the reaction product of apolyamide resin, a solvolytic agent and a titanium catalyst.

Also disclosed is a wire enamel composition comprising the reactionproduct of a polyamide resin, a titanate cast catalyst and a solvolyticagent.

Also disclosed is a method of making magnet wire having at least onelayer of electrically insulating enamel which is a reaction product of apolyamide resin, a titanate catalyst and a solvolytic agent.

Other features and advantages of the present invention will become moreapparent from the following detailed description of the preferredembodiment.

BEST MODE FOR CARRYING OUT THE INVENTION

A solution of the polyamide resin is prepared in the conventional mannerby dissolving the resin in a suitable organic solvent or mixture oforganic solvents. These solvents are generally conventional hydroxylcontaining aromatic hydrocarbons and some typical ones are cresylicacid, phenol, hydrocarbon etc. The preferred solvent is a mixture ofcresylic acid and phenol, typically in concentrations of about 25percent by weight cresylic acid to about 75 percent by weight phenol. Itis preferred that for an enamel which is to be stored or is desired tohave a stable shelf life, that the solvent contain greater than 60percent by weight of phenol.

The polyamide resin may be any polyamide resin useful as magnet wirecoatings. These are usually conventional nylon resins such as nylon 6;nylon 6,6; nylon 11; nylon 12 and aliphatic aromatic nylons such asTrogamide® Nylon (Dynamit-Nobel). The preferred nylon is nylon 6,6because of its high melt point. These nylons are commercially availableand will have molecular weights (weight average) ranging above 25,000and ususally between 25,000 to 40,000 and preferably between 25,000 to35,000. The dissolution of the resin in a solvent is performed usingconventional techniques and equipment. Although almost any concentrationof resin in the solution may be possible to practice this invention, itis most practical to formulate the solution having a resin solidsconcentration from about 10 percent to about 30 percent by weight withabout 20 percent to about 30 percent by weight being preferred.

Once the polyamide resin has been dissolved, the solvolytic agents maybe introduced. These agents will be compounds particularly organic acidshaving at least one active hydrogen which may react with the polyamideresin during the equilibration. The preferred agents are the aliphaticalcohols such as ethylene glycol, however, other materials which may beused are adipic acid, hexamethylene diamine and other polyalcohols oreven water or the actual hydrogen terminated polyamides. The solvolyticagent is generally added in amounts ranging from about 0.5 percent toabout 15 percent by weight of the polyamide resin. It should be notedthat the more solvolytic agent added relative to the polyamide resin,the lower the molecular weight and therefore the viscosity will be ofthe resulting equilibrated resin at reasonable rates. The preferredrange is between about 0.5 percent to about 5 percent by weight of thesolvolytic agent to polyamide resin.

To this solution is then added an organic titanate catalyst such as achelate, alkyl or aromatic titanate. These titanates may be any of theorganic titanates, such as those sold by DuPont Corporation under thetrademark Tyzo® titanates or others. These titanates can be tetra-alkyltitanates having the formula

    Ti(OR).sub.4

where R is an alkyl group typically containing at least three carbonatoms. Examples of titanates such as these are tetra-isopropyl titanate,tetra-N-butyl titanate or tetrakis (2-ethyl hexyl) titanate. Otheruseful titanates can also be aromatic titanates having the formula

    Ti(OR).sub.4

where R is an aromatic group and including polymeric titanates(typically dimers and trimers). Titanates of this variety are cresylic(or phenolic) titanates or their derivatives such as tetra-alkyl (e.g.ethyl, propyl etc.) phenolic, xylenolic, halogenerated phenolic, etc.The dimers and trimers will typically be linear (but may be branched)and chain extended through the --TiO-- group e.g. ##STR4##

However the preferred materials are the titanate chelates such asacetylacetonate tianate, ethyl acetonate titanate, etc. These materialswill have a structure ##STR5## in which X represents a functional groupconsisting oxygen or nitrogen and Y represents a two or three carbonchain, and R is an alkyl group typically containing at least threecarbon atoms. The most preferred titanate is the acetylacetonatetitanates having the structure ##STR6## In addition to these individualtitanates, mixtures of these titanates may also be used.

The titanate catalyst is added to the solution in concentrations ofabout 0.5 percent to about 5 percent by weight based on the weight ofthe resin present in the solution. The preferred concentration is about1 percent to about 2 percent by weight of the polymer resin. All of thereagents should be mixed to a homogenous solution using conventionalmixing or stirring apparatus. The solution is then heated to above itsreaction temperature which is typically above 100° C. and more typicallyin excess of 140° C. with the preferred range being about 140° C. toabout 160° C. The lower limit will be determined by the speed at whichthe reaction takes place (e.g. the lower the temperature the slower thereaction) while the upper temperature limit will be a function of thethermal stability of the reactants.

Although not wishing to be bound by any particular theory, it isbelieved that the hydrolysis takes place as a trans amide esterficationwhich takes place as shown below in reaction 4. ##STR7## wherein x+y=10to 200 and ##STR8## The reaction effectively cleaves the largermolecules of the resin in half thereby reducing the molecular weight inhalf as well. This results in a resin with significantly lowerviscosities at the same solids content. It has been discovered that theuse of the titanates are a critical feature of the equilibration processusing these solvolytic agents. It appears that the titanates act ascatalysts to advance the reaction at a speed which makes the reactionpractical in a production environment. It has been noted that thereaction remains at a virtual standstill irregardless of the temperatureuntil the introduction of the titanates. Once the titanate is added, thereaction advances at a reasonable pace. It has also been noted that themore titanate which is added to the reactants, the faster the reactionadvances.

In determining how far to allow the equilibration process to advancesamples are taken from the reaction vessel periodically. These samplesare then diluted to the predetermined final solids content by a solventmixture of phenol and cresylic acid (other compatible mixtures may beused if desired), and a viscosity measurement is made on the material.When the reaction material reaches the predetermined viscosity at agiven temperature, the reaction is cooled. The solids content andviscosity of the desired final product will, of course, be a function ofthe enameling requirements of a given user and must be determined foreach application. Often, these enameling requirements are closelyrelated to viscosity and therefore the enamels are further diluted usingcompatible solvents, typically phenol or cresylic acid mixtures, toproduce an enamel with a viscosity of about 1,000 centipoise to 45,000centipoise at 86° F. (30° C.) or higher depending on the applicator,with the preferred range being about 2,000 centipoise to about 3,500centipoise at 86° F. (30° C.) and having solids contents between 10percent to 30 percent by weight with the preferred being about 20percent to about 22 percent by weight.

EXAMPLE

To a kettle of the appropriate size (100 gallons) was added 312.4 poundsof a solvent mixture comprised of 25 percent by weight of cresylic acidand 75 percent by weight of phenol. An agitator was turned on and 1.6pounds of tetra acetyl acetonate titanate chelate, 5.3 pounds ofethylene gylcol and 105.6 pounds of reprocessed nylon 6,6 scrap fiber,having an average molecular weight (weight average) of 35,000 were addedto the solvent. The kettle was then purged with nitrogen gas at a rateof 10 standard cubic feet per minute (SCFM) for 15 minutes and thenreduced to 1 SCFM. The contents were then heated, using steam, to atemperature of 150° C.-155° C. Agitation and nitrogen purging werecontinued during the entire equilibration process. After the solutionhad been at temperature for 5 hours, samples were removed every twohours and tested for viscosity until such time as the viscostty reachedthe previously determined set point of 160 centipoise at 86° F. (30°C.). Additionally, the solids content of the solution was determinedfrom every other sample taken.

Once the required viscosity was achieved, the resulting enamel was thendiluted using a mixture of 31 percent by weight of xylene, 15 percent byweight of 150 Hydrocarbon® (Shell Chemical Corporation) and 54 percentby weight of a mixture of phenol and cresylic acid in which the phenolrepresents 75 percent by weight. This formed the final enamel which hada solids content of 21.6 percent by weight and a viscosity of 2,900centipoise at 86° F. (30° C.).

This enamel coating may be applied to magnet wire using conventionalwire enameling techniques and will produce a coating which meets all ofthe industry standards for such enamels. Such processes typically drawthe magnet wire substrate through a die applicator which applies a thinfilm of the enamel to the wire in a uniform manner. The coated wire isthen passed through a curing process, typically an oven, whichevaporates the solvents and cures the enamel forming the insulatinglayer. The wire may then be passed through the applicator again in whichfurther layers of enamel may be applied until the desired thickness ofthe insulating layers has been achieved.

This method for equilibrating polyamide materials offers a number ofimportant advantages over other prior art techniques. First, the processcontains no corrosive, noxious chemical or by-products which could causeproblems with the mixing containers or other metal machinery throughcorrosion. Secondly, the reaction and processing is substantiallysimpler as all of the reagents remain in the final product and nofurther processing is required to remove undesirable side products whichmay impair the effectiveness of the enamel. This single batch methodtherefore saves time and money in preparation. Thirdly, this methodallows for the preparation of a high solids nylon magnet enamel havingviscosities which allow for easy and uniform application to the wiresubstrate using conventional application processes.

It should be understood that the invention is not limited to theparticular embodiments shown and described herein, but that variouschanges and modifications may be made without departing from the spiritand scope of this novel concept as defined by the following claims.

I claim:
 1. A magnet wire enamel comprisnig the reaction product of apolyamide resin, about 0.5 to about 5 percent by weight of said resin ofan organic titanate catalyst selected from the group consisting of (RO₄)Ti, dimers, trimers and mixtures thereof where R is an alkyl group or anaromatic group, and a solvolytic agent comprising an active hydrogencontaining compound capable of cleaving the larger molecules of saidpolyamide resin.
 2. The enamel of claim 1 wherein the polyamide resin ispresent in about 10 percent to about 30 percent by weight based on thesolids content of the enamel.
 3. The enamel of claim 1 wherein thesolvolytic agent is ethylene glycol.